Drier for oils



Patented Sept. 26, 1933 DRIER FOR OILS Herman Alexander Bruson, Philadelphia, Pa.

No Drawing. Application July 27, 1929 Serial No."381,682

19 Claims. (o1.,1a457) My invention relates to driers for oils, paints and varnishes and has for its objectthe provision of a group of compounds which are very efficient I for this purpose. A great many of the members of this group are well known but have never been used for this purpose. There are several, however, that have never been prepared before andit is a further object of my invention to provide a simple process for preparing such new compounds.

I have round that the heavy metal salts, and in,

particular, the manganese, cobalt and lead salts of a benzoic acid, at least one nuclear hydrogen atom of which. 'is replaced by a hydrocarbon radicle, are strikingly efiective as drier's'for oils, paints and varnishes. The metals used for the formation of these salts are polyvalent metals. These substituted benzoic acids include such substances as toluic acid, propyl benzoic acid, isopropyl benzoic acid, butyl benzoic acid (ortho-, metaand para-), I mesitylenic acid, .phenyl benzoic acid (orthometaand para-), naphthoic acid (a and ,8) and their derivatives, that is, those compounds in which at least one hydrogen of the hydrocarbon substituent is replaced by an organic group which may be either an alkyl or an aryl group.

I have found that very good results are obtain able with the heavy metal salts of the toluic acids and their derivatives, wherein at least one hydrogen atom of the methyl group by an organic group, as for example,

P-xylyl-urtho-benzoic acid Napli thyl methylene-ortlio-benzoic acid A H H H OH H H H H COOH H: H:

According to is replaced,

. which may be my invention these-derivatives of toluic acids are prepared by the reduction of organic derivatives ofketo-benzoic acids, which in turn are prepared by condensing practically any organic group or compound containing a replaceable hydrogen with phthalic anhydride in the presence of anhydrous aluminium chloride and hydrolyzing the resulting product.

As starting materials I may use organic derivativesof ortho, meta-, or para-ketobenzoic acids wherein the" carbon atom-ofthe keto group islinked directly to a carbon atom of an'organic radicle. Because of the difliculty encountered in obtaining the paraand meta-keto-benzoic acids, however, I prefer to practice my invention chiefly with the ortho-keto-benaoic" acid which the general structure the carbon atom of the ketoigroup. 1

Practically any 'organic group or cq p umi.

containing a; replaceable hydrogen can be linked V with the'carb'on' atom of the keto group by con'-.

densing said'conipound with phthalic anhydride oritschlorognitroe, alkyl, aryl, or nuclear hydro-1 aluminium chloride. The condensation product genat'ed derivativesinth'e p'resence'of anhydrous so. producedis then hydrolyzedflto, form the fun'- damental body "illustrated by the'structural for mula. shown above.

. :The group or radicle represented by may be an alkyl group or an aryl group,j'whi'ch'term in'-" eludes polynuclearfas Well, as mononuclear "arc;

matic groups and'tlie'ir chloro-, nitro,-'hydroxy, alkyl, aryl, or nuclear hydrogenated derivatives or their ethers. The best results, insofar as the 1 drying of oils,'"paints ,andfvarnishes is concerned, have been produced, generally speaking, 1 with the heavy metal salts of compounds of the above mentioned general structure in-1which Rreprel sents a mononuclear aromatic grouppreferably substitutedby alkyl groups. When R represents an'aromatic groupwhether it be mononuclear or polynuclear, the introductionofhalogen, hydro gen, or alkyl groups into eitherthe nucleus of the phthalic anhydride or the nucleus of the side chain, produces an increase in oil solubilityi' In carryingoutmy invention, I have extended my investigations to the heavy metal salts of the reduction products of derivatives of keto-benzoic acids coon classified in four groups as follows: r a 1 1. Those derivatives in which R. represents an alkyl group such asmethyl, ethyl, butyl, propyl,

ooon 7 coon -Hydrogen'/ with hydrogen gas in the presence of platinum, 1 the hydrogen first saturates'the side chain and then reduces the keto group to a CH2 group as follows: l

coon a-naphthoyl-dbenzoic acid-)Perhydro-naphthyl niethyle'ne-o-benzoic acid I the phthalic anhydride nucleus is substituted by halogens, nitro groups, alkyl groups or hydrogen or unsubstituted. V i

V 2, Those derivatives in which R represents a simple benzene ring and its derivatives, such as benzene, toluene, ethyl benzene, propyl benzene, isopropyl benzene," cymene, dimethyl benzene (xylenes), butyl benzene, amyl benzene, chloro benzene, dichloro-benzene (0, m and p) cyclohexane, methyl-cyclohexane, hexa-ethyl benzene and cyclohexene, wherein'the'phthalic anhydride :11111018115 is substituted or unsubstituted and wherein the keto group is in the ortho, meta, or para position to the carboxyl group.

3. Thosederivativesin which R represents a polynuclear. aromatic group and its derivatives such as naphthalene, chlor-naphthalene, methyl, ethyland isopropyl naphthalene, tetrahydronaph- 1 thalene, 'decahydronaphthalene, anthracene, di-

phenyl, phenanthrene, 'dinaphthyl, ditolyl, retene, perylene, and their aliphatic 'or halogen substituted derivatives, wherein the phthalic an'- hydride nucleus is either substituted or unsubstituted and wherein the keto group is in the ortho, meta, or para position to "the carboxyl group.

rnixed system such as diphenyl oxide, diphenylene oxide, carbazole, anisole, phenetole, dibenzyl ether, dlphenyl methane, dinaphthyl ether; di-

benzyl, ditolyl, dinaphthylene oxide; acenaph- 3 theme, fluorene, chrysene, hydrindene, picenel stilbene, pinene, dipentene and their aliphatic or their halogen substituted derivatives, wherein the phthalic anhydride nucleusis eithersubstituted or' unsubstituted and wherein the ,keto group is,

degreeof reduction varies with the reducing V, agentsfused. For 'example when the reduction is' c'arried out with zinc dust and ammonia, the keto groupl'is reduced to 2. CH2 group and the remainder of the molecule is unchanged, as, for example:

GOOH GOOH p-toluyl-o-benzoic acid p-methyl benzylobenzoic acid When, however, the reduction is carriedout 4. Those derivatives in which R representsa' salts.

These latter reduction products will-bereferred to hereinafter as hydrogenated benz'oic acids, in which at least one nuclear hydrogen atom has been replaced by an organic alipl iatic or aromatic radicle, it being understood that the hen: zene nucleus or/and the side chain maybe hydrogenated. p

The heavy metal salts of the synthetic acids, enumerated above, are prepared by double decomposition of'the water soluble sodium or potassiumsalts of the-latter with a water soluble salt of the heavy metalthat, is desired in the drier, such as, for example, the'chloride, sul-. phate, nitrate or acetate of cobaltor manganese, or with the nitrate or acetate of lead "Incases where the heavy metal salt ofthe synthetic acid is so soluble in water that its recovery, from a water solution is difficult, it may be preferable to prepare the salts by fusion of the heavy metal oxide, hydroxide or carbonate with the synthetic The incorporation of the heavy metal salts of synthetic acids prepared according to my invention in oils, may be accomplished in various many cases, however, it isnecessary'to heat'the oils moderately in order to dissolve the salts. In such cases the salts do not separate out when the oil is cooled to normal temperatures or on long standing. A few of the salts will not dissolve in the oils even at elevated temperatures. Such salts, however, are soluble in aromatic hydrocarbons. Solutions of these salts in aromatic hydrocarbons are miscible with oils without any separation of the salts from the solution.

The following are specific examples of the method of preparing heavy metal salts of the type described and quick drying oils, paints and varnishes obtained by the incorporation of said These examples are purely illustrative and are intended to define the nature of my invention rather than its scope.

. Example 1 I 10 parts of p-xylyl-ortho-benzoic acid our 9113,

-coon. f 1

such as is obtained by the reduction of paratoluyl-o-benzoic acid with-zinc and ammonia (Gresly, Annalen 'der Chemie, 234, 236) is suspended in 100 parts of water and exactly neutralized with sodium hydroxide. The clear solution of the sodium salt thus obtained is then-- treated with an excess of cobaltous sulfate solution whereupon a heavy precipitate is obtained. Filter, wash, and dry. Ablue powder is formed which is soluble in benzene, butyl acetate, acetone, hot linseed oil and-other drying oils in which it behaves as a drier. I v

The manganese salt obtained .by using manganous chloride as above, is a white powder which disperses readily in hot linseed oil, tung oil, perilla oil and other drying oils.

The lead salt, prepared by using excess lead acetate solution as. above, behaves similarly. U

. rxampze z imparts of alpha naphthyl methylene-orthobenzoic acid i OOOH such as is obtained by reducing naphthoyl-ortho-benzoic acid with zinc and ammonia} are 1 suspended in water and neutralized with sodium hydroxide. By adding cobaltous sulfate, manganous chloride, or lead acetate solution, the cor-. responding heavy metal salts are precipitated. After beingwashed and dried these salts may be used as driers in oils, being soluble in warm linseed oil, tung oil and the like.

Example 3 10 parts of perhydro-para-xylyl-ortho-benzo- H2 such as is obtained by the reduction of paraxyloyl-o-benzoic acid with hydrogen in the presence of platinum is neutralized with sodium hydroxide solution and its cobalt, manganese, and lead salts prepared by double decomposition, as described above. These salts are soluble in linseed oil, tung oil and other drying oils and act as driers therein.

Example 4 Perhydro-naphthyl methylene-ortho benzoic acid,

such as is obtained by reducing naphthoyl-o-benzoic acid with hydrogen and platinum, (Willstaetter, Ber. der Deutschen Chem. Ges. 54, 1420) when converted into its cobalt, manganese, and lead salts as described above, gives oil soluble compounds which are eflicient driers for oils such as linseed, tung, perilla, soya bean, and the like. The heavy metal salts of this acid have heretofore been prepared by Willstaetter (above reference) but their solubility inidryin'g' oils and their drying action therein, is new.

7 heavy metal s'altsof these acids and others of the same class,enumer- I have found thati'the other ated above,'are also soluble in fatty oils; I These include the zinc, aluminium, chromium, iron; va-tnadium, cadmium, tin, nickel andcopper salts.

l or the drying of oils, thequantity of salt to be added depends upon thesmeta'lli'c content and the nature of the. metal present.

.0l-0.05% of cobalt or manganese or 0.2% of lead: relative to the weight of the oil is sufficient. The

In general from saltsare best incorporated by heating the .oil'to about 450 F. and sprinkling the :finelypowdered material therein. r 7 I havefoundthat the solubility of :these salts in.

oils is greatly dependent upon the nature ofathe group R. In general the introduction of alkyl groups or of hydrogen in Rporin thebenzoic acid nucleus gives increasedoil solubility.

iThe simple alkylon arylsubstituted benzoic acids such as ortho-toluic acid, para-ethyl benzoic. acid'and phenyl benzoic acid, yield heavy metal salts which are not quite as readily incorporated in hot drying oilsas are those heavy metal salts derived from the substituted .toluic acids,'examples of which are given above. The introduction into linseed oil of .05% cobalt in the form of cobalt-para-xyly1-ortho-benzoate cuts down thedrying. time from 18. hours to':4

hours.

The advantage of usingthese salts in oils,.instead of the heavy metal salts at present employed in the art, such as the rosinates, acetates, borates, and linoleates, is that lighter colored varnishes and oil compositions maybe obtained from the former. a

It is of course apparent to those skilled in the; 7

art that not only drying oils, but also fattyv acids derived from such such oils, as well as resinous products derived therefrom, such as oil varnishes,

paints, synthetic resins, andthe like may be dried;

at an accelerated rate by incorporating therein any of the driers described above.

Having thus described my invention and illustrated several embodiments of the practical application thereof, what I claim as new and desire to secure by Letters Patent isz- 1. A method for accelerating the drying of: oxidizable oils and of paints, varnishes, and resin compositions derivedtherefrom, which comprises incorporating therein, as a siccative, a polyvalent metal salt of a toluic acid in which one hydrogen atom of the methyl group is replaced by a hydrocarbon radicle.

2. A method for accelerating the drying of oxicompositions derived therefrom which comprises incorporating therein, as a siccative, a polyvalent metal salt of a toluic acid in which one hydizable oils and of paints, varnishes, and resin drogen atom of the methyl group is replaced by an aliphatic hydrocarbon radicle.

3. A method for accelerating the drying of oxi- 1 atom of ...the; methyl group isreplacedby an aralkyl group.

v 5. A'method for drying oxidizable oil compositions as set forth in claim 1 in which the metal salt used is one of the group consisting of lead,- ,cobalt'and manganese salts and mixtures of such salts.

. 6. A'method for drying oxidizable oil compositions .as set forth in claim 2 in which the 'metal salt .used is one of the group consisting of lead, cobalt and manganese salts and mixtures of such salts.

'7. A method for drying oxidizable oil compositions'as set forth in claim 3 in which the metal compositions derived therefrom which comprises incorporating therein, as a siccative, a polyvalent metal salt 'of a member selected from the group consisting of butylbenzoic acid, amylbenzoic acid, benzylbenzoic' acid, naphthyl-methylene-benzoic acid and their homologues and nuclear hydro genated derivatives.

- 10. A method for. accelerating the drying of oxidizable oils, and of paints, varnishes and resin compositions derived therefrom which comprises incorporating therein/as a siccative, asalt of amylbenzoic acid in which the metal radicle is a member selected from the group consisting'of lead, cobalt, and manganese.

' 11. A composition of vmatter comprising a substance selected from the group consisting of oxidizable oils, paints and varnishes derived there- 7 from and oxidizable resins and a polyvalent metal salt of a toluic acid in which one hydrogen atom of the methyl group is replaced by a hydrocarbon radicle. I

12. A composition of matter comprising-a substance selected from the group consisting of oxidizable oils, paints and varnishes derived therefrom and oxidizable resins and apolyvalent metal salt of a toluic acid in which one hydrogen atom of the methyl group is replaced by an aliphatic hydrocarbon radicle.

. '13. A composition of mattercomprising {a substance selected .fromthe groupconsisting of oxidizable oils, paints and varnishesderived there from andoxidizable resins and apolyvalent metal.

salt of a. toluic acid in which .one hydrogen atom of. the methyl group is replaced by an aryl group;

. 14. A composition of matter comprising a sub..

stance selected from the. group consisting ofoxidizable oi1s,.paints and varnishes derived there-1 from and oxidizab'le resins and a polyvalent metal salt of; a toluic acid in which one hydrogen atom of. the methyl group isreplaced. by anaralkylv gIOLlp. f., '.2 15. A composition'of matter 'comprisingasub-s stance'selected from the group consisting of oxidizable oils, paints and varnishesderived there-.

from and oxidizable resins and a polyvalent metal salt of a member selected from the group consisting of butylbenzoic acidyamylbenz oic acid, benzylbenzoic acid, naphthyl-methylene-benzoic acid and the homologues' and nuclear hydrogenated derivatives thereof. g

16. A composition of matter as set'forth in claim 11 in which the polyvalent metal is one' selected from the group consisting of lead, cobalt and manganese.

1'7. A composition of matter as set .forth in claim 15 in which the polyvalent metal 'is one selected from'the group consisting of lead,'cobalt and manganese.

183A method for accelerating thejdrying' of oxidizable oils and of paints ,,varnishes and resin compositions derived therefrom, which comprises incorporating therein, asa' siccative, a polyvalent metal' salt of a' toluic acid in which one hydrogen atom of themethyl' group is replaced by an aralkyl group and in which said polyvalent metal is one selected from the class consisting of cobalt and manganese 19. A composition of matter comprising a polyvalent metal salt of a toluic acid in which one hydrogen atom of the methyl group is replaced by an aralkyl group and in which the polyvalent metal is one selected from the class consisting of cobalt and manganese, and a substance selected from the group consisting of oxidizable oils, paints'and varnishes derived there-.

from and oxidizable resins.

f H RMAN ALEXANDER BRUsoN. 

